Anticorrosion means and compositions containing same

ABSTRACT

This invention relates to a corrosion inhibitor for protecting metallic surfaces which are in contact with water, in particular circuits, apparatus and devices which use water as energetic or thermic fluid, said corrosion inhibitor being a fluorophosphate compound selected from the group consisting of: 
     (i) compound of the formula M 2   I  PO 3  F, xH 2  O 
     (ii) compound of the formula LiM I  PO 3  F, xH 2  O 
     (iii) compound of the formula NaM I  PO 3  F, xH 2  O 
     (iv) compound of the formula M II  PO 3  F, xH 2  O 
     (v) compound of the formula M 2   I  M II  (PO 3  F) 2 , xH 2  O 
     (vi) compound of the formula M I  PO 2  F 2 , xH 2  O 
     (vii) compound of the formula M II  (PO 2  F 2 ) 2 , x H 2  O 
     (wherein M I  is Na, K, Rb, Cs or HN 4  ; M II  is Mg, Ca, Ba, Sr, Zn, Cd, Mn, Ni or Co; and x is an integer or a fractional number comprised between 0 and 6) and 
     (viii) mixtures thereof.

This application is a continuation of application Ser. No. 497,572 filed May 24, 1983, now abandoned.

The present invention relates to a new corrosion inhibitor belonging to the fluorophosphate family, for protecting metallic surfaces, particularly those of installations and devices using water as energetic or thermic fluid. The invention also relates to a composition containing this inhibitor in association, if necessary, with one or more other substances useful in the domain of protection against aqueous corrosion.

It is known that any metallic surface currently used in industry and any equipment composed of one or more metals such as iron and its alloys, particularly galvanized steel, copper and its alloys, aluminum and its alloys, to mention only those most employed, are subjected, upon contact with water, to the phenomena of corrosion which are all the greater and more accumulative as fresh water is supplied frequently or in large quantities in installations, circuits or devices using water as energetic or thermic fluid.

A certain number of technical solutions have been proposed in the past to solve the problem of the protection of metallic surfaces against corrosion. Among recent solutions which have proved effective are those described in European Patent No. 10485 and in European Patent Application No. 81400861 which employ compositions containing either at least one polyamine and at least one alkylenephosphonic acid derivative, or at least one polyamine and at least one organic polyelectrolyte resulting from polymerization or copolymerization of a monomer having a C═C double bond.

Furthermore, it is known, particularly by U.S. Pat. No. 4,132,572, that fluorophosphates (also known as "oxyfluorinated derivatives of phosphorus 5") are substances known to be means for treating metallic surfaces before painting.

According to the invention, a new technical solution for solving the problem of protecting metallic surfaces against aqueous corrosion is recommended, which employs new inhibitor means which are structurally different from the means previously known in the domain of corrosion inhibition.

This new solution is particularly advantageous for protecting from aqueous corrosion the metallic surfaces of installations, circuits and devices using liquid water (raw water, demineralized water, synthetic water, industrial water which may in particular contain an antifreeze, salt water such as sea water, aqueous mud, particularly for oil drilling, etc. . .) as energetic or thermic fluid (cooling or heating circuits).

The new corrosion inhibitor according to the invention which belongs to the family of fluorophosphates is characterized in that it is selected from the group consisting of:

(i) compound of the formula M₂ ^(I) PO₃ F, xH₂ O

(ii) compound of the formula LiM^(I) PO₃ F, xH₂ O

(iii) compound of the formula NaM^(I) PO₃ F, xH₂ O

(iv) compound of the formula M^(II) PO₃ F, xH₂ O

(v) compound of the formula M₂ ^(I) M^(II) (PO₃ F)₂, xH₂ O

(vi) compound of the formula M^(I) PO₂ F₂, xH₂ O and

(vii) compound of the formula M^(II) (PO₂ F₂)₂, xH₂ O (wherein M^(I) is Na, K, Rb, Cs or HN₄ ; M^(II) is Mg, Ca, Ba, Sr, Zn, Cd, Mn, Ni or Co; and x is an integer or a fractional number comprised between 0 and 6) and

(viii) mixtures thereof.

The preferred corrosion inhibitors according to the invention are zinc and potassium fluorophosphates, namely ZnPO₃ F and K₂ PO₃ F, the most interesting being ZnPO₃ F.

The fluorophosphates according to the invention are substances which are generally sparingly water-soluble, the threshold of solubility in water being of the order of 10 g/l.

This weak water-solubility is not a hindrance having regard to the quantities to be used. In fact, it has been observed that, to protect the metallic surfaces against aqueous corrosion, a dose of 3 to 500 ppm of inhibitor according to the invention should be used, and preferably a dose between 5 and 200 ppm, particularly for ZnPO₃ F. On this subject, it is noted that, with respect to raw water A and synthetic water B described hereinafter, the dose of ZnPO₃ F giving maximum inhibition is from 20 to 25 ppm (cf. Table III hereinbelow).

According to an embodiment of the invention, a corrosion inhibitor is recommended which is characterized in that it contains in solution or aqueous suspension a corrosion inhibitor selected from the group of the fluorophosphates of (i) to (viii) hereinabove. This composition is used so that, after introduction into the corrosive aqueous fluid, the content of the inhibitor is from 3 to 500 ppm by dry weight (preferably from 5 to 200 ppm by weight particularly for ZnPO₃ F) with respect to the weight of the fluid.

According to another embodiment of the invention, an anti-corrosion composition is recommended which comprises, in association in water:

A - a corrosion inhibitor selected from the family of fluorophosphates as defined hereinabove, and

B - a substance selected particularly from the group consisting of polyamines, organic polyelectrolytes resulting from polymerization or copolymerization of a monomer having a C═C double bond, alkylenepolyphosphonic acid derivatives, aminoalkylenephosphonic acid derivatives and mixtures thereof.

With respect to the use of means A and B alone, the association of A and of B presents a synergy concerning the inhibition of corrosion.

Among substances B which may be used, the means described in the European Patent and the European Patent Application mentioned above and mixtures thereof may be employed.

Among suitable polyamines, those responding to the general formula

    R--NH-(CH.sub.2).sub.m ].sub.n NH.sub.2                    (I)

(wherein R is a saturated or unsaturated aliphatic C₁₂ -C₂₂ hydrocarbon radical, m represents an integer between 2 and 8 inclusive and n represents an integer between 1 and 7 inclusive), and mixtures thereof are recommended.

The amines of formula I may be used as found on the market, alone or mixed with one another, in their pure or technical forms. Polyamines prepared from fatty acids of animal, vegetable or synthetic origin may also be used. Among suitable polyamines on the market, particular mention may be made of the products known under the trade names DUOMEEN, DINORAM, TRINORAM, POLYRAM, LILAMIN and CEMULCAT which contain at least one polyamine according to formula I. Among the latter products, particular mention may be made of "DINORAM O" which contains approximately 75% by dry weight of oleylamino-propyleneamine, 9% by dry weight of stearylaminopropyleneamine and 6% by dry weight of hexadecylaminopropyleneamine, and "DINORAM S" which contains approximately 43% by dry weight of stearylaminopropyleneamine, 28% by dry weight of oleylaminopropyleneamine and 28% by dry weight of hexadecylaminopropyleneamine, these products being marketed by the firm CECA.

Among the polyelectrolytes which may be used as substances B, polymeric organic polyelectrolytes having a molecular weight greater than or equal to about 150 and preferably a molecular weight greater than or equal to 300 are recommended. The upper limit of the molecular weight may be very high, and in particular of the order of 2 000 000 or more. Among suitable polyelectrolytes, particular mention may be made of the polymers and copolymers obtained from acrylic acid, its esters and salts, methacrylic acid, its esters and salts, acrylamide, methacrylamide, maleic acid, esters and salts thereof.

These polyelectrolytes are generally polymer substances obtained by polymerization, copolymerization or terpolymerization from a monomer which may be schematically represented by the formula ##STR1## in which M₁, M₂, M₃ or M₄, which may be identical or different, each represent an atom of hydrogen, a C₁ -C₄ alkyl group, or a cyano, aldehyde, alcohol, amine, amide, imine, imide, ammonium, CO₂ M or SO₃ M group (where M is H, C₁ -C₄ alkyl, NH₄ ⁺ or a metallic cation, particularly Na⁺ or K⁺).

The definitions given hereinabove for formula II encompass the copolymers obtained from ethylene and its ethylenic analogs (M₁, M₂, M₃ and M₄ each representing H or alkyl). However, to obtain polymers and copolymers of the acrylic, acrylate, acrylamide, acrylaldehyde, acrylonitrile, maleic type in particular, it is clear that at least one of the M₁, M₂, M₃ and M₄ is different from H and the C₁ -C₄ alkyl group, in the formula of monomer II.

The preferred polyelectrolytes are mentioned hereinafter, namely:

(i) the derivatives of the polyacrylic type responding to the general formula ##STR2## (wherein R₁ is H, C₁ -C₄ alkyl, Na⁺, K⁺ or NH₄ ⁺, R₂ is H or C₁ -C₄ alkyl and n₁ is an integer higher than or equal to 2) and mixtures thereof;

(ii) the derivatives of the polymaleic type responding to the general formula ##STR3## (wherein R₃ and R₄, which may be identical or different, each represent an atom of hydrogen or a C₁ -C₄ alkyl group, and R₁ and n₁ are defined as indicated above) and mixtures thereof;

(iii) the derivatives of the polyacrylamide type responding to the general formula ##STR4## (wherein R₂ and n₁ are defined as indicated above) and mixtures thereof;

(iv) the copolymer derivatives of the acrylic-acrylamide type schematically presenting a moeity ##STR5## (wherein R₁, R₃ and R₄ are defined as indicated above, n₂ is an integer higher than or equal to 1, and n₃ and n₄, which are identical or different, are integers higher than or equal to 1, one of the n₃ and n₄ being able to represent 0 in the case of a sequenced copolymer) and mixtures thereof;

(v) the copolymer derivatives of the styrene-maleic type schematically presenting a moeity ##STR6## (wherein R₁, n₂, n₃ and n₄ are defined as indicated above) and mixtures thereof.

(vi) the copolymer derivatives of the acrylic-acrylamide type schematically presenting a moeity ##STR7## (wherein R₁, R₃, R₄, n₂, n₃ and n₄ are defined as indicated hereinabove) and mixtures thereof.

Among the suitable aminoalkylenephosphonic and alkylenepolyphosphonic acid derivatives, particular mention may be made of the acids of formula III.1, III.2 and III.3 hereinafter, their esters and salts, and mixtures thereof, namely:

(i) the aminoalkylenephosphonic acids of the general formula ##STR8## (wherein n₅ represents an integer included between 0 and 4; and n₆ represents an integer included between 1 and 6), their salts with mono- or polyvalent metallic ions, such as Na⁺, K⁺, NH₄ ⁺ ; one of the preferred products of formula III.1 being the sodium aminotrimethylenephosphonate (where n₅ is 0)

(ii) the alkylenediphosphonic acids, their esters and salts, such as in particular 1-hydroxyethylidene-1,1-diphosphonic acid of formula ##STR9## and its salts of sodium, potassium or ammonium; and

(iii) the aminoalkylenepolyphosphonic acids of formula ##STR10## (wherein Alk is a C₁ -C₆ alkylene group, and n₇ is an integer included between 0 and 3), their metal or ammmonium salts.

Table I hereinafter gives a certain number of examples of corrosion inhibitors according to the invention. These examples which are in no way limiting have been given solely by way of illustration.

                  TABLE I                                                          ______________________________________                                                                        Quantity                                        Ex-                            (parts by                                       ample Means                    dry weight)                                     ______________________________________                                         Ex. 1 fluorophosphate of zinc (ZnPO.sub.3 F)                                                                  1                                               Ex. 2 fluorophosphate of potassium                                                                            1                                                     (K.sub.2 PO.sub.3 F)                                                     Ex. 3 ZnPO.sub.3 F             10                                                    aminotrimethylenephosphonate of                                                                         10                                                    potassium                                                                      oleyaminopropyleneamine  2                                               Ex. 4 ZnPO.sub.3 F             5                                                     aminotrimethylenephosphonate                                                                            10                                                    of potassium                                                                   oleyaminopropyleneamine  2                                               Ex. 5 ZnPO.sub.3 F             2.5                                                   aminotrimethylenephosphonate of sodium                                                                  10                                                    stearylaminoethyleneamine                                                                               2                                               Ex. 6 ZnPO.sub.3 F             10                                                    polyacrylic acid (PMM = 700)                                                                            10                                                    polyacrylate of sodium (PMM = 700)                                                                      40                                              Ex. 7 ZnPO.sub.3 F             5                                                     polyacrylic acid (PMM = 500)                                                                            10                                                    polyacrylate of sodium (PMM = 2500)                                                                     40                                              Ex. 8 ZnPO.sub.3 F             10                                                    polyacrylic acid (PMM = 750)                                                                            50                                              Ex. 9 K.sub.2 PO.sub.3 F       10                                                    aminotrimethylenephosphonate of                                                                         15                                                    potassium                                                                Ex. 10                                                                               ZnPO.sub.3 F             2.5                                                   aminotrimethylenephosphonate of potassium                                                               15                                              ______________________________________                                          Note:                                                                          PPM = mean molecular weight                                              

The products of Examples 1 and 2 are put in the form of aqueous compositions by suspending ZnPO₃ F or K₂ PO₃ F in water; a composition containing 12 g/l of ZnPO₃ F or K₂ PO₃ F will be used which is diluted at the moment of use in the corrosive medium. The products of Examples 3-7 are prepared by introducing ZnPO₃ F in the mixture of the other two means, said mixture having been obtained according to the modi operandi described in the European Patent and European Patent Application mentioned above. The products of Examples 8-10 are prepared by introducing in water ZnPO₃ F or K₂ PO₃ F with polyacrylic acid or potassium aminotrimethylenephosphonate.

When a composition containing a means A and a substance B is used, a composition comprising:

1 to 15 parts by weight of means A, and

1 to 100 parts by weight of substance B will advantageously be employed.

The tests carried out with the products according to the invention have been summarized hereinafter.

I - Direct measurement of the corrosion by determining the loss of weight of test pieces (a) Equipment and modus operandi

The equipment and modus operandi relative to the determination of the loss of weight of the test pieces by direct measurement of the gravimetric type, are those described in European Patent No. 10485 mentioned above.

Tests were undertaken on test pieces made of steel, copper and/or aluminium with raw water "A" (drilling water) and synthetic water "B" which is very corrosive due to the presence of chlorides and dissolved oxygen obtained by total demineralization of the raw water "A" by passage over ion exchanger resins then addition of 200 mg/l of sodium chloride. Waters A and B had the following characteristics given in Table II.

                  TABLE II                                                         ______________________________________                                         Characteristics                                                                              Raw water "A"                                                                               Synthetic water "B"                                 ______________________________________                                         pH            6.6          7.2                                                 Hydrotimetric titer TH                                                                       12° French                                                                           0° French                                    Alkalimetric titer TA                                                                        0° French                                                                            0° French                                    Full alkalimetric titer                                                                      5.6° French                                                                          0.5° French                                  TAC                                                                            Strong acid titer TAF                                                                        8.2° French                                                                          17° French                                   Sodium (in Na.sup.+)                                                                         5.8 mg/l     78.6 mg/l                                           Chlorides (in Cl.sup.-)                                                                      1.3° French                                                                          121.3 mg/l                                          Sulfates (in SO.sub.4.sup.--)                                                                6° French                                                                            0° French                                    Nitrates (in NO.sub.3.sup.-)                                                                 0.87° French                                                                         0° French                                    Iron (in Fe.sup.++)                                                                          0.15 mg/l    0° French                                    Oxygen        saturation   saturation                                          Resistivity (Ω · cm.sup.-1)                                                   7840         2495                                                ______________________________________                                    

Measurement of the loss of weight was carried out in tests of the "heat" type and of the "cold" type. To simplify reading of the results, the loss of weight has been translated into speed of corrosion V (expressed in μ/p.a.) and into inhibitory efficiency E% (percentage of inhibition) according to the relations

    V=(P×365)/(J×S×d)

in which

V=speed of corrosion in μ/p.a. (ie. in μ/year)

P=loss of weight in mg

J=number of days of exposure to the agressive medium

S=outer surface of the test piece in μ²

d=specific mass of the metal of the test piece in mg/μ³ ; and

    E%=[(Vo-V)/Vo]×100

in which Vo and V respectively represent the speeds of corrosion (expressed in μ/p.a.) without and with inhibitor.

(b) Results

The results obtained are shown in Tables III, IV and V hereinbelow.

These results show that the fluorophosphates according to the invention and their associations with polyamines, aminoalkylenepolyphosphonic acid derivatives, and/or organic polyelectrolytes inhibit very effectively the aqueous corrosion of metallic surfaces.

                  TABLE III                                                        ______________________________________                                         Corrosion tests of the "cold" type                                             corrosive medium: synthetic water B                                            temperature: 20° C.                                                     duration of the tests: 50 hrs.                                                 Product              corrosion                                                         dose (in ppm)                                                                               steel                                                     Nature    (a)            μ/p.a.                                                                               E %                                          ______________________________________                                         control   0              1142     0                                            Example 1 6.25           223      80.67                                                  12.5           39.5     96.54                                                  25             16.5     98.54                                                  50             74.3     93.49                                                  100            83.2     98.11                                                  200            74.3     93.49                                        Example 3 50             42.5     96.28                                                  100            55.4     95.15                                        Example 4 50             43       96.23                                                  100            62.5     94.53                                        Example 5 50             50.1     95.61                                                  100            51.9     95.46                                        Example 6 60             122.1    89.31                                        Example 7 55             89.7     92.15                                        Example 8 52.5           142.2    87.55                                        Example 9 60             95       91.68                                        Example 10                                                                               55             230.7    79.86                                        ______________________________________                                          Note                                                                           (a) = dose in dry matter                                                 

                  TABLE IV                                                         ______________________________________                                         Corrosion tests of the "cold" type                                             corrosive medium: raw water A                                                  temperature: 20° C.                                                     duration: 50 hrs.                                                              Product                                                                        dose        Corrosion                                                          (in ppm)    Steel      Copper     Aluminum                                     Nature (a)      μ/p.a.                                                                              E %  μ/p.a.                                                                            E %  μ/p.a.                                                                            E %                              ______________________________________                                         Control                                                                                0       1264    0    7     0    28    0                                Example                                                                                5       145.7   88.47                                                                               5.54  20.86                                                                               20.5  26.79                            1      10       17.7    98.60                                                  Example                                                                               50       9.4     99.26                                                                               2.1   70   14.8  47.14                            ______________________________________                                          Note                                                                           (a) = dose expressed in dry matter                                       

                  TABLE V                                                          ______________________________________                                         Corrosion tests of the "heat" type                                             corrosive medium: raw water A                                                  temperature: 50° C.                                                     duration: 50 hrs.                                                              Product                                                                        dose       Corrosion                                                           in ppm     Steel      Copper     Aluminum                                      Nature (a)     μ/p.a.                                                                              E %  μ/p.a.                                                                            E %  μ/p.a.                                                                            E %                               ______________________________________                                         Control                                                                                0      1550     0   25     0   38     0                                Example                                                                               125     542.5   65   14.75 41   0.84  82                                2      250     434     72   8.75  65   4.94  87                                       500     75.5    95   0.25  83   0.76  98                                ______________________________________                                          Note                                                                           (a) = dose expressed in dry matter                                       

II - Study of the inhibition of aqueous corrosion by means of ZnPO₃ F as a function of the pH

With the synthetic water B described hereinabove, the inhibition of the aqueous corrosion of steel test pieces by means of ZnPO₃ F (product of Example 1) as a function of the pH was studied. The technique of measuring the loss of weight of the test pieces, on the one hand, and the determination of the speed of corrosion and the anticorrosive effectiveness, on the other hand, which was carried out is that used above.

In these tests ZnPO₃ F was used at the dose of 25 ppm. The results are shown in Table VI.

                  TABLE VI                                                         ______________________________________                                         Corrosion tests as a function of the pH                                        Agressive medium: synthetic water B                                            Corrosion inhibitor: ZnPO.sub.3 F at the dose of 25 ppm                        temperature: 20° C.                                                     duration: 50 hrs.                                                                                Corrosion                                                                      steel                                                        Product   pH            μ/    E %                                           ______________________________________                                         Control   7.2 (a)       1142     0                                             ZnPO.sub.3 F                                                                             7.2 (a)       16.5     98.5                                                    8 (b)         35.4     96.9                                                    9 (b)         23       97.9                                                    10 (b)        5.84     99.5                                          ______________________________________                                          Notes                                                                          (a) pH without addition of NaOH                                                (b) pH adjusted by addition of NaOH                                      

III - Inhibition of the corrosion of an oil well

Into the annular space of a steel oil well operating in pumping mode and having a length of 2500 meters are injected the products of Examples 1, 3 and 6 in the aqueous mud so that the content of the products of said examples is included between 20 and 150 ppm. It is observed that the speed of corrosion expressed in μ/p.a. is considerably reduced with the products of Examples 1, 3 and 6 with respect to the control (injection of aqueous mud alone). 

What is claimed is:
 1. A method for protecting metallic surfaces which are in contact with a corrosive aqueous energic or thermic fluid and tend to be corroded thereby which comprises incorporating in said fluid between 3 and 500 ppm by weight of a fluorophosphate compound corrosive inhibitor selected from the group consisting of:(i) compound of the formula M₂ ^(I) PO₃ F, xH₂ O (ii) compound of the formula LiM^(I) PO₃ F, xH₂ O (iii) compound of the formula NaM^(I) PO₃ F, xH₂ O (iv) compound of the formula M^(II) PO₃ F, xH₂ O (v) compound of the formula M₂ ^(I) M^(II) (PO₃ F)₂, xH₂ O (vi) compound of the formula M^(I) PO₂ F₂, xH₂ O (vii) compound of the formula M^(II) (PO₂ F₂)₂, xH₂ O and (viii) mixtures thereof ;wherein M^(I) is Na, K, Rb, Cs or HN₄ ; M^(II) is Mg, Ca, Ba, Sr, Zn, Cd, Mn, Ni or Co; and x is an integer or a fractional number comprised between 0 and
 6. 2. A method according to claim 1 in which the corrosion inhibitor is zinc fluorophosphate.
 3. A method according to claim 1 in which the corrosion inhibitor is potassium fluorophosphate.
 4. A method according to claim 1 in which said corrosive fluid also contains a substance (B) selected from the group consisting of polyamines, organic polyelectrolytes resulting from polymerization and copolymeriation of a monomer having a C═C double bond, alkylenephosphonic acid derivatives, aminoalkylene phosphonic acid derivatives and mixtures thereof.
 5. A method according to claim 4 in which there is from 1-100 parts dry weight of substance (B) per from 1-15 parts dry weight of fluorophosphate.
 6. A method according to claim 1 in which the corrosive fluid contains zinc fluorophosphate in an amount between 5 and 200 ppm by weight. 